U.S. patent number 11,384,207 [Application Number 17/428,705] was granted by the patent office on 2022-07-12 for preparation of a cured polymer comprising urethane groups and silicon atoms.
This patent grant is currently assigned to BASF SE. The grantee listed for this patent is BASF SE. Invention is credited to Peter Rudolf, Indre Thiel, Thomas Maximilian Wurm.
United States Patent |
11,384,207 |
Thiel , et al. |
July 12, 2022 |
Preparation of a cured polymer comprising urethane groups and
silicon atoms
Abstract
A process prepares a cross-linked polymer containing urethane
groups and silicon atoms. Starting materials of the process include
a compound A) with a five-membered cyclic monothiocarbonate group,
a compound B) with an amino group, selected from primary or
secondary amino groups or blocked amino groups, and optionally, a
compound C) with at least one functional group that reacts with a
group --SH. One of the compounds contains a silicon-functional
group. In one example of the process, compounds A) and B), and
optionally C), are then reacted under exclusion of water to obtain
a polymer with curable silicon-functional groups. The polymer is
applied to a surface, gap, or a three-dimensional template. The
silicon-functional groups are cured with ambient water. The polymer
contains 0.001 to 0.3 mol of silicon per 100 g of the polymer.
Inventors: |
Thiel; Indre (Ludwigshafen,
DE), Wurm; Thomas Maximilian (Ludwigshafen,
DE), Rudolf; Peter (Ludwigshafen, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
N/A |
DE |
|
|
Assignee: |
BASF SE (Ludwigshafen am Rhein,
DE)
|
Family
ID: |
1000006425143 |
Appl.
No.: |
17/428,705 |
Filed: |
February 7, 2020 |
PCT
Filed: |
February 07, 2020 |
PCT No.: |
PCT/EP2020/053083 |
371(c)(1),(2),(4) Date: |
August 05, 2021 |
PCT
Pub. No.: |
WO2020/161281 |
PCT
Pub. Date: |
August 13, 2020 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20220041815 A1 |
Feb 10, 2022 |
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Foreign Application Priority Data
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|
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Feb 8, 2019 [EP] |
|
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19156254 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
77/26 (20130101); C07F 7/1892 (20130101); C07F
7/18 (20130101); C09J 135/02 (20130101); C08F
220/387 (20200201); C09D 183/10 (20130101); C07D
327/04 (20130101); C08F 222/22 (20130101); C07F
7/0814 (20130101); C08F 222/1063 (20200201); C09J
133/14 (20130101); C08G 77/458 (20130101); C08G
71/04 (20130101); C08G 77/28 (20130101); C08F
2810/50 (20130101); C08F 2810/20 (20130101); C08F
2800/20 (20130101); C08F 2800/10 (20130101) |
Current International
Class: |
C08G
77/458 (20060101); C08G 77/26 (20060101); C08F
222/22 (20060101); C08F 222/10 (20060101); C08F
220/38 (20060101); C09D 183/10 (20060101); C08G
77/28 (20060101); C09J 133/14 (20060101); C09J
135/02 (20060101); C07D 327/04 (20060101); C08G
71/04 (20060101); C07F 7/18 (20060101); C07F
7/08 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1 506 964 |
|
Feb 2005 |
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EP |
|
2468791 |
|
Jun 2012 |
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EP |
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WO 98/26005 |
|
Jun 1998 |
|
WO |
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WO-2012/003187 |
|
Jan 2012 |
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WO |
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2018/042030 |
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Mar 2018 |
|
WO |
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WO-2019/034468 |
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Feb 2019 |
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WO |
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WO-2019/034469 |
|
Feb 2019 |
|
WO |
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WO-2019/034470 |
|
Feb 2019 |
|
WO |
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WO-2019/034473 |
|
Feb 2019 |
|
WO |
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Other References
US. Appl. No. 16/639,339, filed Feb. 14, 2020, 2020/0354333, Rudolf
et al. cited by applicant .
International Search Report dated Apr. 30, 2020 in
PCT/EP2020/053083. cited by applicant .
Written Opinion dated Apr. 30, 2020 in PCT/EP2020/053083. cited by
applicant .
Reynolds et al., "Mercaptoethylation. II. Preparation of
2-Mercaptoethyl Carbamates and Oligoethylene Sulfides," Journal of
Organic Chemistry, vol. 26, No. 12, Dec. 1961, pp. 5111-5115. cited
by applicant .
U.S. Office Action dated Mar. 28, 2022 in U.S. Appl. No.
16/639,204, 14 pages. cited by applicant .
U.S. Office Action dated May 6, 2022 in U.S. Appl. No. 16/639,339,
15 pages. cited by applicant.
|
Primary Examiner: Zimmer; Marc S
Attorney, Agent or Firm: Gruneberg and Myers PLLC
Claims
The invention claimed is:
1. A process for the preparation of a substrate applied with a
cross-linked polymer, comprising urethane groups and silicon atoms,
the process comprising: a) providing a compound A), a compound B),
and optionally a compound C), for a reaction according to b1) to
b2), c1) to c2), or d1) to d3), wherein the compound A) comprises
at least one five-membered cyclic monothiocarbonate group, wherein
the compound B) comprises at least one amino group, selected from
the group consisting of primary amino groups, secondary amino
groups, blocked primary amino groups, and blocked secondary amino
groups, wherein the compound C), if present, comprises at least one
functional group that reacts with a group --SH, and whereby at
least one of compounds A), B), and optionally C) comprises a
silicon-functional group; b1) reacting compounds A) and B), and
optionally C), under exclusion of water to obtain a polymer with
silicon-functional groups that are still curable, and b2) applying
the polymer obtained in b1) to a surface, gap, or a
three-dimensional template, and curing the silicon-functional
groups with ambient water; or, alternatively, c1) applying
compounds A) and B), and optionally C), to a surface, gap, or a
three-dimensional template, and c2) reacting compounds A) and B),
and optionally C), and curing the silicon-functional groups with
ambient water in one step; or, alternatively, d1) applying the
compound A) with a silicon-functional group, the compound B) with a
silicon-functional group, the compound C) with a silicon-functional
group, or a mixture comprising compounds A) and C) or B) and C),
whereby such mixture does not comprise compounds A) and B) in
combination, to a surface, gap, or a three-dimensional template,
and d2) curing the silicon-functional groups with ambient water,
and d3) adding compounds A), B), and optionally C), which have been
provided but not yet applied and reacting these compounds.
2. The process according to claim 1, wherein the compound A) is a
compound of formula (I) ##STR00016## with R.sup.1a to R.sup.4a
independently from each other representing hydrogen or an organic
group with up to 50 carbon atoms, whereby, alternatively, R.sup.2a,
R.sup.4a, and the two carbon atoms of the thiocarbonate group
together form a five to ten membered carbon ring; or a compound of
formula (II) ##STR00017## with R.sup.1b to R.sup.4b independently
from each other representing hydrogen or an organic group with up
to 50 carbon atoms, whereby, alternatively, R.sup.2b, R.sup.4b, and
the two carbon atoms of the monothiocarbonate group together form a
five to ten membered carbon ring, and with one of the groups
R.sup.1b to R.sup.4b being a linking group to Z, n representing an
integral number of at least 2, and Z representing a n-valent
organic group.
3. The process according to claim 1, wherein the compound B)
comprises one to five amino groups.
4. The process according to claim 1, wherein the at least one
functional group of compound C) that reacts with --SH is selected
from the group consisting of a non-aromatic, ethylenically
unsaturated group and an epoxy group.
5. The process according to claim 1, wherein the compound B)
comprises the silicon-functional group.
6. The process according to claim 1, wherein the silicon-functional
group is an alkoxysilane group of formula
--SiR.sup.1sR.sup.2sR.sup.3s, wherein at least one of the groups
R.sup.1s to R.sup.3s is an alkoxy group and the other groups
R.sup.1s to R.sup.3s are hydrogen or an alkyl group.
7. The process according to claim 6, wherein two or three of the
groups R.sup.1s to R.sup.3s are an alkoxy group and a remaining
group R.sup.1s to R.sup.3s, if present, is an alkyl group.
8. The process according to claim 1, wherein a mixture of compounds
A), B), and optionally C) is liquid at 21.degree. C. and 1 bar.
9. The process according to claim 1, wherein b1) to b2) are
performed.
10. The process according to claim 1, wherein a content of silicon
in the cross-linked polymer comprising urethane groups and silicon
atoms is 0.001 to 0.3 mol silicon per 100 g of the polymer.
11. A coating, a sealed material, or a molded body, obtainable by
the process as defined in claim 1.
12. A polymer, obtained by reacting a compound A), a compound B),
and optionally a compound C), wherein the compound A) comprises at
least one five-membered cyclic monothiocarbonate group, wherein the
compound B) comprises at least one amino group, selected from the
group consisting of primary amino groups, secondary amino groups,
blocked primary amino groups, and blocked secondary amino groups,
and wherein the compound C), if present, comprises at least one
functional group that reacts with a group --SH; wherein at least
one of compounds A), B), and optionally C), comprises a
silicon-functional group, and wherein the polymer comprises 0.001
to 0.3 mol of silicon per 100 g of the polymer.
13. A compound, comprising one or two five-membered cyclic
monothiocarbonate groups and one alkoxysilane group
--SiR.sup.1sR.sup.2sR.sup.3s, wherein at least one of the groups
R.sup.1s to R.sup.3s is an alkoxy group and the other groups
R.sup.1s to R.sup.3s are hydrogen or an alkyl group.
14. The compound according to claim 13, wherein the compound is a
compound of formula (IV) ##STR00018## wherein at least one of the
groups R.sup.1s to R.sup.3s is an alkoxy group, and the other
groups R.sup.1s to R.sup.3s are hydrogen or an alkyl group, and
wherein Sp is a spacer group, which is an organic group with 1 to
20 carbon atoms.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the National Stage entry under .sctn. 371 of
International Application No. PCT/EP2020/053083, filed on Feb. 7,
2020, and which claims the benefit of priority to European
Application No. 19156254.5, filed on Feb. 8, 2019. The content of
each of these applications is hereby incorporated by reference in
its entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
Object of the present invention is a process for the preparation of
a cross-linked polymer comprising urethane groups and silicon
atoms, wherein
a) a compound A) with at least one five-membered cyclic
monothiocarbonate group and a compound B) with at least one amino
group, selected from primary or secondary amino groups or blocked
primary or secondary amino groups, hereinafter referred to as amino
groups, and optionally a compound C) with at least one functional
group that reacts with a group --SH are used as starting
materials,
whereby at least one of the compounds used as starting material
comprises a silicon-functional group,
and wherein compounds A), B) and optionally C) are processed as
follows by
b1) reacting compounds A) and B) and optionally C) under exclusion
of water to obtain a polymer with silicon-functional groups that
are still curable and
b2) applying the polymer obtained in b1) to a surface, gap or a
three-dimensional template and curing the silicon-functional groups
with ambient water
or, alternatively,
c1) applying the compounds A) and B) and optionally C) to a
surface, gap or a three-dimensional template and
c2) reacting the compounds and curing the silicon-functional groups
with ambient water in one step,
or, alternatively,
d1) applying a compound A) with a silicon-functional group or a
compound B) with a silicon-functional group or a compound C) with a
silicon-functional group or a mixture of such a compound with
further compounds A) to C), whereby such mixture does not comprise
compounds A) and B) in combination, to a surface, gap or a
three-dimensional template and
d2) curing the silicon-functional groups with ambient water and
d3) then adding the missing compounds A), B) and optionally C) and
reacting these compounds.
Description of Related Art
Polyurethanes are important industrial polymers. They have very
good mechanical properties and are therefore used in many technical
applications, for example, as foam or as binder in coatings or
adhesives.
Polyurethanes have been modified with silyl groups, which are
notably alkoxysilane groups. Such silyl-modified polyurethanes are
moisture curable and have been used, for example, as one-component
binder or resin in coatings or adhesives.
According to U.S. Pat. No. 3,632,557 silicon-terminated
polyurethanes are obtained by reacting an isocyanate terminated
prepolymer with an aminosilane.
U.S. Pat. Nos. 4,625,012 and 6,355,127 B1 disclose the use of
isocyanato-organosilanes to obtain silyl-modified
polyurethanes.
In WO 2012/003187 A1 silicon compounds with a hydrogen-silicon bond
and a cross-linkable group are used to modify polyurethanes.
There is a demand to find alternative polymers with urethane groups
and moisture curable silyl groups. Alternative polymers may
comprise, for example, additional heteroatoms or functionalities
which improve the technical application of such polymers or allow
to extend the field of technical applications.
There is also a demand to find new processes for the preparation of
silyl-modified polyurethanes, notable processes that does not
involve the use of isocyanates.
The object of EP 2468791 A1 are epoxy compositions that comprise
compounds with five-membered cyclic ring systems comprising oxygen
and sulfur.
D. D. Reynolds, D. L. Fields and D. L. Johnson, Journal of Organic
Chemistry, 1961, page 5111 to 5115, disclose compounds with a
five-membered cyclic monothiocarbonate ring system and reactions
thereof. Inter alia a reaction with an amino compound is
mentioned.
WO 2019/034468 A1 and WO 2019/034469 A1 relate to a process for the
synthesis of compounds with at least one monothiocarbonate
group.
WO 2019/034470 A1 and WO 2019/034473 A1 relate to polymers which
are obtained by reacting compounds with at least one
monothiocarbonate group.
SUMMARY OF THE INVENTION
It was an object of this invention to provide alternative
silyl-modified polymers and an alternative process for the
preparation of silyl-modified polyurethanes. The alternative
process should be economic and flexible, thus allowing the easy
preparation of silyl-modified polyurethanes suitable for a variety
of technical applications.
Accordingly, a process and silyl modified polymers comprising
urethane and thioether groups have been found.
The invention relates to a process for the preparation of a
cross-linked polymer comprising urethane groups and silicon atoms,
wherein
a) a compound A) with at least one five-membered cyclic
monothiocarbonate group and a compound B) with at least one amino
group, selected from primary or secondary amino groups or blocked
primary or secondary amino groups, hereinafter referred to as amino
groups, and optionally a compound C) with at least one functional
group that reacts with a group --SH are used as starting
materials,
whereby at least one of the compounds used as starting material
comprises a silicon-functional group, and
wherein compounds A), B) and optionally C) are processed as follows
by
b1) reacting compounds A) and B) and optionally C) under exclusion
of water to obtain a polymer with silicon-functional groups that
are still curable and
b2) applying the polymer obtained in b1) to a surface, gap or a
three-dimensional template and curing the silicon-functional groups
with ambient water,
or, alternatively,
c1) applying the compounds A) and B) and optionally C) to a
surface, gap or a three-dimensional template and
c2) reacting the compounds and curing the silicon-functional groups
with ambient water in one step,
or, alternatively,
d1) applying a compound A) with a silicon-functional group or a
compound B) with a silicon-functional group or a compound C) with a
silicon-functional group or a mixture of such a compound with
further compounds A) to C), whereby such mixture does not comprise
compounds A) and B) in combination, to a surface, gap or a
three-dimensional template and
d2) curing the silicon-functional groups with ambient water and
d3) then adding the missing compounds A), B) and optionally C) and
reacting these compounds.
In a further aspect, the invention relates to coatings, sealed
materials or molded bodies obtainable by the process, as defined
herein.
In a further aspect, the invention relates to a polymer derived of
compounds A), B) and optionally C) comprising 0.001 to 0.3 mol of
silicon per 100 g of the polymer.
In a further aspect, the invention relates to a compound comprising
one or two five-membered cyclic monothiocarbonate groups and one
alkoxysilane group --SiR.sup.1sR.sup.2sR.sup.3s.
DETAILED DESCRIPTION OF THE INVENTION
To compound A)
Compound A) comprises at least one five-membered cyclic
monothiocarbonate group.
The five-membered cyclic monothiocarbonate group is a ring system
with 5 members, three of them are from the monothiocarbonate
--O--C(.dbd.O)--S-- and the further two members are carbon atoms
closing the five-membered cycle.
Compound A) may be a low molecular compound or a polymeric compound
and may comprise, for example, up to 1000, notably up to 500,
preferably up to 100 five-membered cyclic monothiocarbonate
groups.
In a preferred embodiment, compound A) comprises one to three
cyclic monothiocarbonate groups.
In a most preferred embodiment, compound A) comprises one or two
five-membered cyclic monothiocarbonate groups.
Preferred compounds A) have a molecular weight of up to 10000
g/mol, notably up to 5000 g/mol and particularly up to 1000 g/mol.
Most preferred are compounds A) having a molecular weight of up to
500 g/mol.
Compounds A) may comprise other functional groups, for example,
non-aromatic, ethylenically unsaturated groups, ether groups,
thioether groups or carboxylic ester groups or a silicon-functional
group.
In a preferred embodiment, compounds A) do not comprise other
functional groups than cyclic monothiocarbonate groups,
non-aromatic, ethylenically unsaturated groups, ether groups,
thioether groups or carboxylic ester groups or silicon-functional
groups.
Preferred compounds A) are compounds of formula (I)
##STR00001##
with R.sup.1a to R.sup.4a independently from each other
representing hydrogen or an organic group with up to 50 carbon
atoms, whereby, alternatively, R.sup.2a, R.sup.4a and the two
carbon atoms of the thiocarbonate group may also together form a
five to ten membered carbon ring;
or compounds of formula (II)
##STR00002##
with R.sup.1b to R.sup.4b independently from each other
representing hydrogen or an organic group with up to 50 carbon
atoms, whereby, alternatively, R.sup.2b, R.sup.4b and the two
carbon atoms of the monothiocarbonate group may also together form
a five to ten membered carbon ring, and with one of the groups
R.sup.1b to R.sup.4b being a linking group to Z,
n representing an integral number of at least 2, and
Z representing a n-valent organic group.
To compounds A) of formula (I)
Compounds A) of formula (I) have one five-membered cyclic
monothiocarbonate group, only.
In case that any of R.sup.1a to R.sup.4a represent an organic
group, such organic group is preferably an organic group with up to
30, more preferably up to 20 carbon atoms. In a further preferred
embodiment R.sup.2a and R.sup.4a do not form a five to ten membered
carbon ring together with the two carbon atoms of the thiocarbonate
group.
In case that any of R.sup.1a to R.sup.4a represent an organic
group, such organic group may comprise heteroatoms and functional
groups as listed above. In particular, it may comprise oxygen,
nitrogen, sulfur, silicon and chloride. R.sup.1a to R.sup.4a may
comprise oxygen, for example, in form of ether groups, hydroxy
groups, aldehyde groups, keto groups or carboxy groups. In a
preferred embodiment, the organic group is an aliphatic organic
group with up to 30 carbon atoms which may comprise oxygen,
nitrogen or chloride, in particular oxygen.
The term "halogenide", as used herein, is the trivial name of a
covalently bonded halogen atom, preferably a Cl atom.
The term "chloride", as used herein, is the trivial name of a
covalently bonded Cl atom.
In a more preferred embodiment, the organic group is selected from
an alkyl group, from a group --CH.sub.2--O--R.sup.5a or a group
--CH.sub.2--O--C(.dbd.O)--R.sup.6a or a group
--CH.sub.2--NR.sup.7aR.sup.8a with R.sup.5a to R.sup.8a being an
organic group with up to 30 carbon atoms, preferably up to 20
carbon atoms. In particular, R.sup.5a to R.sup.8a represent an
aliphatic or aromatic group, which may comprise oxygen, for
example, in form of ether groups. In a preferred embodiment,
R.sup.5a to R.sup.8a represent an aliphatic hydrocarbon group, such
as an alkyl group with 1 to 10 carbon atoms, an alkoxy group or a
poly-alkoxy group. In a most preferred embodiment, R.sup.5a to
R.sup.8a represent an aliphatic hydrocarbon group, notably an alkyl
group with 1 to 10 carbon atoms.
In a most preferred embodiment, the organic group is a group
--CH.sub.2--O--R.sup.5a or a group
--CH.sub.2--O--C(.dbd.O)--R.sup.6a.
Preferably, two to all four of R.sup.1a to R.sup.4a in formula (I)
represent hydrogen, and the remaining groups R.sup.1a to R.sup.4a
represent an organic group.
More preferably, two or three of R.sup.1a to R.sup.4a in formula
(I) represent hydrogen, and the remaining groups R.sup.1a to
R.sup.4a represent an organic group.
Most preferably, three of R.sup.1a to R.sup.4a in formula (I)
represent hydrogen, and the remaining group of R.sup.1a to R.sup.4a
represents an organic group. In a preferred embodiment, R.sup.1a or
R.sup.2a is the remaining group representing an organic group.
As preferred compounds A) with one five-membered cyclic
monothiocarbonate group may be mentioned, for example, compounds A)
of formulae
##STR00003##
The substituent "C.sub.12/C.sub.14" means a substituent derived
from C.sub.12/C.sub.14 fatty alcohol.
To compounds A) of formula (II)
Compounds A) of formula (II) have at least two five-membered cyclic
monothiocarbonate groups.
In case that any of R.sup.1b to R.sup.4b represent an organic
group, such organic group is preferably an organic group with up to
30 carbon atoms. In a further preferred embodiment, R.sup.2b and
R.sup.4b do not form a five to ten membered carbon ring together
with the two carbon atoms of the thiocarbonate group.
In case that any of R.sup.1b to R.sup.4b represent an organic
group, such organic group may comprise other elements than carbon
and hydrogen. In particular, it may comprise oxygen, nitrogen,
sulfur, silicon and chloride. In a preferred embodiment, the
organic group may comprise oxygen or chloride. R.sup.1b to R.sup.4b
may comprise oxygen, for example, in form of ether groups, hydroxy
groups, aldehyde groups, keto groups or carboxy groups.
One of the groups R.sup.1b to R.sup.4b is the linking group to
Z.
Preferably, the linking group is simply a bond or a group
CH.sub.2--, CH.sub.2--O-- or CH.sub.2--O--C(.dbd.O)-- or
CH.sub.2--NR.sup.5b-- with R.sup.5b being an aliphatic group,
notably an alkyl group with at maximum 20 carbon atoms.
More preferably, the linking group is simply a bond or a group
CH.sub.2-- or a group CH.sub.2--O-- or a group
CH.sub.2--O--C(.dbd.O)--.
In a most preferred embodiment, the linking group is a group
CH.sub.2--O--.
Preferably, two or three of the groups R.sup.1b to R.sup.4b in
formula (II) are hydrogen.
In a most preferred embodiment, three of the groups R.sup.1b to
R.sup.4b represent hydrogen, and the remaining group of R.sup.1b to
R.sup.4b is the linking group to Z.
In a most preferred embodiment, groups R.sup.1b or R.sup.2b is the
linking group to Z.
n represents an integral number of at least 2. For example, n may
be an integral number from 2 to 1000, specifically from 2 to 100,
respectively 2 to 10.
In a preferred embodiment, n is an integral number from 2 to 5, in
particular n is 2 or 3.
In a most preferred embodiment, n is 2.
Z represents a n-valent organic group. In case of a high number of
n, such as, for example, 10 to 1000, Z may be a polymeric group, in
particular a polymer-backbone, obtained, for example, by
polymerization or copolymerization, such as radical polymerization
of ethylenically unsaturated monomers, polycondensation or
polyaddition. For example, polyesters or polyamides are obtained
via polycondensation under elimination of water or alcohol, and
polyurethanes or polyureas are obtained via polyaddition.
Such compounds of formula (II) are, for example, polymers obtained
by radical polymerization or copolymerization of ethylenically
unsaturated monomers comprising monothiocarbonate groups or of
monomers comprising epoxy groups which are then transferred into a
monothiocarbonate group.
In a preferred embodiment, Z is a n-valent organic group with up to
50 carbon atoms, in particular up to 30 carbon atoms, and which may
comprise other elements than carbon and hydrogen, and n is an
integral number from 2 to 5, notably 2 or 3, most preferred 2.
In a particularly preferred embodiment, Z is a n-valent organic
group with up to 50 carbon atoms, in particular up to 30 carbon
atoms, and which comprises carbon, hydrogen and optionally oxygen,
only and no further elements, and n is an integral number from 2 to
5, notably 2 or 3, most preferred 2.
In a preferred embodiment, Z is a polyalkoxylene group of formula
(G1) (V--O--).sub.mV
wherein V represents a C.sub.2-C.sub.20-alkylene group, and m is an
integral number of at least 1. The terminal alkylene groups V are
bonded to the linking group, which is one of the groups R.sup.1b to
R.sup.4b, see above.
Preferably, the C.sub.2-C.sub.20-alkylene group is a
C.sub.2-C.sub.4-alkylene group, in particular ethylene or
propylene. m may, for example, be an integral number from 1 to 100,
in particular from 1 to 50.
In a further preferred embodiment, Z is a group of formula (G2)
##STR00004##
wherein W is a bi-valent organic group with at maximum 10 carbon
atoms, and n is 2, and R.sup.10b to R.sup.17b independently from
each other represent H or a C.sub.1-C.sub.4-alkyl group, and
wherein the two hydrogen atoms in the para position to W are
replaced by the bond to the linking group, which is one of the
groups R.sup.1b to R.sup.4b, see above.
Preferably, at least six of R.sup.10b to R.sup.17b are hydrogen. In
a most preferred embodiment, all of R.sup.10b to R.sup.17b are
hydrogen.
Groups W are, for example:
##STR00005##
Preferably, W is an organic group that consists of carbon and
hydrogen, only.
Most preferred W is
##STR00006##
which corresponds to the structure of bisphenol A.
In a further preferred embodiment, Z is a group G3, wherein G3
represents an alkylene group, notably a C.sub.2-C.sub.8-alkylene
group; preferred examples of such an alkylene group are ethylene
(CH.sub.2--CH.sub.2), n-propylene (CH.sub.2--CH.sub.2--CH.sub.2)
and notably n-butylene
(CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2).
Compounds A) with at least two five-membered cyclic
monothiocarbonate groups are, for example, compounds of formula
(III)
##STR00007##
wherein G represents an alkylene group with 2 to 10, notably 2 to 6
carbon atoms.
A preferred compound of formula (III) is
bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)]
which has the formula
##STR00008##
Compound A) may be a mixture of different compounds A). Compound
A), respectively the mixture of compounds A), is liquid at
21.degree. C., 1 bar. In one preferred embodiment, the liquid
compound A) is obtained by solving a compound A) which is solid at
21.degree. C., 1 bar in a compound A) which is liquid at 21.degree.
C., 1 bar.
In a preferred embodiment, compound A) is liquid at 21.degree. C.,
1 bar.
To the synthesis of compounds A)
Some methods for the synthesis of compounds with one
monothiocarbonate group are described in the state of the art.
According to U.S. Pat. Nos. 3,072,676 and 3,201,416 ethylene
monothiocarbonates may be prepared by a two-step-process. In a
first step mercaptoethanol and chloro-carboxylates are reacted to
give hydroxyethylthiocarbonate, which is heated in the second step
in the presence of a metal salt catalyst to the ethylene
monothiocarbonate.
According U.S. Pat. No. 3,517,029 alkylene monothiocarbonates are
obtained by reacting mercaptoethanol and a carbonate diester in the
presence of a catalytically active salt of thorium.
According to the process disclosed in U.S. Pat. No. 3,349,100
alkylene monothiocarbonates are obtained by reacting an epoxide
with carbonyl sulfide. The availability of carbonyl sulfide is
limited. Yields and selectivities of alkylene monothiocarbonates
obtained are low.
A synthesis using phosgene as starting material is known from U.S.
Pat. No. 2,828,318. Phosgene is reacted with hydroxymercaptanes.
Yields of monothiocarbonates are still low, and by-products from
polymerization are observed.
A preferred process for the preparation of compounds A) and C) is a
process, wherein
a) a compound with at least one epoxy group (shortly referred to as
epoxy compound) is used as starting material;
b) the compound is reacted with phosgene or an alkyl chloroformate
thus giving an adduct; and
c) the adduct is reacted with a compound comprising anionic sulfur
to give the compound with at least one five-membered cyclic
monothiocarbonate groups.
This process is in detail described in WO 2019/034469 A1.
To compound B)
Compound B) is a compound with at least one amino group, selected
from a primary or a secondary amino group. In this patent
application the word "amino group" shall mean a primary or
secondary amino group, if not indicated otherwise or obvious from
the content otherwise.
Compounds B) do not comprise any monothiocarbonate groups.
Compound B) may have, for example, a molecular weight of up to
500,000 g/mol. The latter might be the case if compound B) is a
high molecular compound such as a polymer comprising amino groups.
In case of a polymer the term "molecular weight" means the number
average molecular weight Mn, as determined by GPC against
polystyrene as standard.
Compound B) may be, for example, a urethane groups comprising
adduct obtained by reacting compounds with cyclic monothiocarbonate
groups and compounds with primary or secondary amino groups,
whereby the amino groups are in stoichiometric excess compared to
the monothiocarbonate groups, thus giving a urethane groups
comprising adduct which still has primary or secondary amino groups
but no monothiocarbonate groups.
Preferred compounds B) have a molecular weight of up to 10000
g/mol, notably of up to 5000 g/mol and particularly of up to 1000
g/mol. Most preferred are compounds B) having a molecular weight of
from 60 g/mol to 500 g/mol.
Compounds B) may comprise, for example, polymerizable,
ethylenically unsaturated groups, ether groups, carboxylic ester
groups or silicon-functional groups.
In a preferred embodiment, compounds B) do not comprise any other
functional groups than primary or secondary amino groups, tertiary
amino groups, polymerizable, ethylenically unsaturated groups,
ether groups or silicon-functional groups.
In a preferred embodiment, compounds B) comprise 1 to 10 amino
groups, preferably 1 to 5, respectively 1 to 3 amino groups, and,
in a most preferred embodiment, compound B) comprises 1 to 2 amino
groups.
In a preferred embodiment, at least one of the amino groups of
compound B) is a primary amino group.
In a most preferred embodiment, all amino groups of compound B) are
primary amino groups.
Compounds B) with one amino group are, for example, monoalkylamines
with a primary amino group such as C.sub.1-C.sub.20-alkylamines or
cycloalkyl-amines or etheramines such as 2-methoxyethylamine or
3-methoxypropylamine or di- or polyether amines such as di- or
polyglycol amine or polyoxypropylene amine.
Compounds B) with more than one amino group are, for example,
alkylene diamines or alkylene polyamines such as ethylene diamine,
propylene diamine, butylene diamine, pentamethylene diamine,
hexamethylene diamine, neopentane diamine, octamethylene diamine,
1,3-diaminopentane, or 2-methylpentan-1,5-diamine; alkylene
diamines or alkylene polyamines comprising ether groups
(polyetheramine) such as polyglycol diamine or polyoxypropylene
diamine; cycloaliphatic diamines, such as cyclohexyldiamines, for
example, 1,2-diaminocyclohexane, 1-methyl-2,4-diaminocyclohexane,
1-methyl-2,6-diaminocyclohexane or mixtures thereof, isophorone
diamine, bis(4-amino-cyclohexyl)-methane,
1,3-bis(aminomethyl)-cyclohexane, 1,4-bis(aminomethyl)-cyclohexane,
2,5-bisaminomethyl tetrahydrofuran, or
3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane; aromatic diamines,
such as 1,2-phenylene-diamine or 1,4-phenylene-diamine, toluene
diamines, 4,4'-diamino-diphenylmethane,
4,4'-diaminodiphenylsulfone, or 2,5-bisaminomethyl furan.
Compounds B) may also be used in a form, wherein the amino groups
are protected with a protecting group. As soon as it becomes
necessary or desired the protecting group is removed so that the
compounds B) above with free amino groups are obtained. Usually,
removal of the protecting groups occurs under the conditions of the
reaction. Usual protected amino groups for amino groups are, for
example, ketimines, aldimines, imidazolidines, oxazolidines, lewis
acid complexed amines, carbamates, benzyloxycarbonyl amines,
acyloximes, or formanilides. The deprotecting reaction can, for
example, be triggered by either temperature, light, pH or the
presence of water/humidity.
Further suitable compounds B) are, for example, listed in WO
2019/034470 A1 and WO 2019/034473 A1.
Compound B) may be a mixture of different compounds B).
To compound C)
Compounds C) are compounds with at least one functional group that
reacts with a thiol group --SH.
Compounds C) do not comprise five-membered cyclic monothiocarbonate
groups and do not comprise amino groups.
Compounds C) may have, for example, a molecular weight of up to
500,000 g/mol. The latter might be the case if compound C) is a
high molecular compound such as a polymer.
Preferred compounds C) have a molecular weight of up to 10000
g/mol, notably of up to 5000 g/mol and particularly of up to 1000
g/mol. Most preferred are compounds C) having a molecular weight of
from 60 g/mol to 500 g/mol.
Compounds C) may have, for example, up to 1000 functional groups
that react with a group --SH, notably up to 500 and preferably up
to 100 functional groups that react with a group --SH.
In a preferred embodiment, compound C) comprises 1 to 10, notably 2
to 6 functional groups that react with a group --SH.
In a most preferred embodiment, compound C) comprises 2 or 3
functional groups that react with a group --SH.
In a preferred embodiment, the reaction of the functional group of
compound C) with the group --SH results in the formation of a
sulfur-carbon bond.
The reaction of the functional group of compound C) with the group
--SH may be an addition reaction, a condensation reaction or a
nucleophilic substitution reaction.
Compounds C), that undergo an addition reaction with the group --SH
are, for example, compounds with non-aromatic, ethylenically
unsaturated groups or compounds with epoxy groups or compounds with
isocyanate groups as functional groups. Non-aromatic, ethylenically
unsaturated groups are non-aromatic carbon-carbon double bonds or
carbon-carbon triple bonds.
Compounds C), that undergo a condensation reaction with the group
--SH are, for example, compounds with carbonyl groups as functional
group, for example, monocarbonyl compounds or dicarbonyl compounds
such as dialdehydes or diketones.
Compounds C), that undergo a nucleophilic substitution reaction
with the group --SH are, for example, compounds with a halogenide,
notably chloride, as functional group.
Preferred functional groups that react with a group --SH are
non-aromatic, ethylenically unsaturated groups or epoxy groups.
Preferred examples of a polymerizable, ethylenically unsaturated
group are the vinyl group H.sub.2C.dbd.CH--, the olefinic group
--HC.dbd.CH--, wherein the two carbon atoms of the double bond are
each substituted by one hydrogen, only, and the further
substituents are notably carbon atoms, including carbon atoms of a
cyclic system, and the acrylic or methacrylic group, shortly
referred to as (meth)acrylic group. In this patent application the
term "vinyl group" does not include the (meth)acrylic group.
Particularly preferred compounds C) are compounds with vinyl
groups, (meth)acrylic groups or epoxy groups.
Compounds with vinyl groups, (meth)acrylic groups or epoxy groups
are well known.
Suitable compounds C) are listed, for example, in WO 2019/034470 A1
and WO 2019/034473 A1.
Compound C) may be a mixture of different compounds C).
To the silicon-functional group
At least one of the compounds reacted comprises a
silicon-functional group.
In case that compounds A) and B) are reacted, at least one of
compounds A) or B) comprises a silicon-functional group.
In case that compounds A), B) and C) are reacted, at least one of
compounds A), B) or C) comprises a silicon-functional group.
More than one compound of A) and B), respectively A), B) and C) may
comprise a silicon-functional group. Usually only one of the
compounds reacted will be a compound comprising a
silicon-functional group.
As mentioned already above, compounds A), B) and C) may be mixtures
of different compounds A), B) and C). Hence, the desired content of
silicon-functional groups in the polymer obtained from compounds
A), B) and optionally C) can easily be obtained by using mixtures
of compounds with silicon-functional groups and without
silicon-functional groups.
In a preferred embodiment, compounds B) comprise a
silicon-functional group.
The silicon-functional group is preferably a group with at least
one silicon atom and at least one group that is cross-linkable
through a silanol cross-linking reaction.
The silicon-functional group may comprise more than one silicon
atoms. The silicon atoms may be bonded to each other directly or
via an oxygen bridge. In a preferred embodiment, the
silicon-functional group comprises 1 to 3 silicon atoms. Most
preferred are silicon-functional groups with only one silicon
atom.
Groups that are cross-linkable through a silanol cross-linking
reaction are preferably the hydroxy group and hydrolysable groups,
notably alkoxy groups; alkoxy groups are preferred, notably
C.sub.1-C.sub.10-alkoxy groups.
The silicon-functional group may comprise more than one group which
is cross-linkable through a silanol cross-linking reaction. The
possible number of groups which are cross-linkable through a
silanol cross-linking reaction depends on the number of silicon
atoms in the silicon-functional group.
The silicon-functional groups may, in addition, comprise hydrogen
or alkyl groups that are bonded to the silicon atoms. In a
preferred embodiment, the silicon-functional groups may comprise
alkyl groups but does not comprise hydrogen that is bonded to the
silicon atoms.
Preferably, the silicon-functional groups do not comprise any other
constituents than silicon, groups which are cross-linkable through
a silanol cross-linking reaction, hydrogen or alkyl groups that are
all bonded to silicon and oxygen as possible bridge between silicon
atoms.
Most preferably, the silicon-functional group is an alkoxysilane
group of formula --SiR.sup.1sR.sup.2sR.sup.3s
wherein at least one of the groups R.sup.1s to R.sup.3s is an
alkoxy group, and the other groups R.sup.1s to R.sup.3s are
hydrogen or an alkyl group.
The alkoxy group is preferably a C.sub.1-C.sub.10-alkoxy group,
notably a C.sub.1-C.sub.4-alkoxy group, for example, a butoxy
group, a propoxy group, a ethoxy group or a methoxy group. Most
preferably, the alkoxy group is an ethoxy group or methoxy
group.
The alkyl group is preferably a C.sub.1-C.sub.10-alkyl group,
notably a C.sub.1-C.sub.4-alkyl group, for example, a butyl group,
a n-propyl group, an ethyl group or a methyl group. Most
preferably, the alkyl group is an ethyl group or a methyl
group.
Preferably, two or three of the groups R.sup.1s to R.sup.3s are an
alkoxy group, and the remaining groups R.sup.1s to R.sup.3s are
hydrogen or an alkyl group.
More preferably, two or three of the groups R.sup.1s to R.sup.3s
are an alkoxy group, and any remaining group R.sup.1s to R.sup.3s
is an alkyl group.
Most preferably, all three groups R.sup.1s to R.sup.3s are alkoxy
groups.
Preferred compounds A) with a silicon-functional group comprise one
or two five-membered cyclic monothiocarbonate groups, particularly
one five-membered cyclic monothiocarbonate group, and one
alkoxysilane group --SiR.sup.1sR.sup.2sR.sup.3s.
Particularly preferred compounds are compounds of formula (IV)
##STR00009##
wherein R.sup.1s to R.sup.3s have the meaning above, and Sp is a
spacer group, which is an organic group with 1 to 20, notably 1 to
10, preferably 1 to 6, notably 1 to 3 carbon atoms.
Sp may comprise other atoms than carbon and hydrogen, for example,
nitrogen, oxygen or sulfur. Preferably, Sp is a hydrocarbon group
that may comprise oxygen, for example, in form of ether groups, but
no other heteroatoms. In a particularly preferred embodiment, Sp is
an alkylene group with 1 to 20, notably 1 to 10 and most preferably
1 to 6, notably 1 to 3 carbon atoms.
A specific example of a compound of formula (IV) is the compound
below:
##STR00010##
Preferred compounds B) with a silicon-functional group comprise one
or two amino groups, particularly one amino group, and one
alkoxysilane group --SiR.sup.1sR.sup.2sR.sup.3s.
An example of compound B) with a silicon-functional group is
trimethoxysilylpropyl amine.
Preferred compounds C) with a silicon-functional group comprise one
or two functional groups, particularly one functional group, that
react with a group --SH and one alkoxysilane group
--SiR.sup.1sR.sup.2sR.sup.3s.
Examples of compounds C) with a silicon-functional group are
trimethoxysilylpropyl methacrylate and trimethoxysilylpropyl
glycidylether.
To the process
According to the process of this invention,
a compound A) with at least one five-membered cyclic
monothiocarbonate group, and
a compound B) with at least one amino group, selected from primary
or secondary amino groups or blocked primary or secondary amino
groups, hereinafter referred to as amino groups, and optionally a
compound C) with at least one functional group that reacts with a
group --SH are used as starting materials,
whereby at least one of the compounds used as starting material
comprises a silicon-functional group.
The principles of the reaction of compounds A), B) and optionally
C) as well as details of the parameters of the reaction are
described in WO 2019/034470 A1 and WO 2019/034473 A1.
The ring system of the five-membered cyclic monothiocarbonate group
of compound A) is opened by the amino group of compound B),
resulting in an adduct comprising a urethane group and a group
--SH.
The group --SH of the adduct may be further reacted with a --SH
reactive group, notably a non-aromatic ethylenically unsaturated
group or an epoxy group of compound C) or also of compounds A) and
B) as there exist also compounds A) or B) that comprise a
non-aromatic, ethylenically unsaturated group, for example,
5-(methacryloyloxy)methyl-1,3-oxathiolane-2-one or
5-(acryloyloxy)methyl-1,3-oxathiolane-2-one (compounds C), allyl
amine or aminoalkylvinylether (compounds B).
The group --SH reacts with the --SH reactive group. For example,
the addition of a non-aromatic, ethylenically unsaturated group to
--SH is known as Michael addition or thiol-ene reaction.
It should be mentioned that groups --SH that are not reacted may
oxidize and will form disulfide bridges. Such oxidation may occur
at room temperature in the presence of oxygen or other oxidants.
Disulfide bridges may improve mechanical properties of the polymers
obtained.
The obtained polymer comprises as structural element a urethane
group with a sulfur atom being bonded via an ethylene group to the
oxygen of the urethane group. This structural element can be
represented by the following formula:
##STR00011##
The variables A to E represent any possible substitutions by
substituents.
The following statements apply to each of the three process
alternatives b1) to b2) or, alternatively c1) to c2) or
alternatively d1) to d3):
Compounds B) are preferably used in an amount to have 0.8 to 1.2
mol of amino groups of compound B) per 1 mol of five-membered
cyclic monothiocarbonate groups of compound A) in the reaction
mixture.
Preferably, the amount of functional groups that react with --SH is
0.5 to 1.2 mol per 1 mol of five-membered cyclic monothiocarbonate
groups of compound A).
Preferably, the functional groups that react with --SH are groups
of compound C).
Preferably, the starting materials are compounds A), B) and C).
Examples for combinations of compounds A), B) and C) that are
reacted in the process steps are listed below, whereby the
functional groups are abbreviated as follows:
Cyclic monothiocarbonate group of compound A): CTC
Primary amino group of compound B: PA
Functional group that reacts with --SH of compound C), A) or B):
FG
Silicon-functional group: SIL a compound A) with two CTC, a
compound B) with one PA and one SIL and a compound C) with one to
five FG, preferably 2 to 5 FG; a compound A) with two CTC, a
compound B) with at least two PA and a compound C) with one FG
(unsaturated group) and one SIL; a compound A) with two CTC, a
compound B) with at least two PA and a compound C) with one FG
(epoxy group) and one SIL; a compound A) with two CTC, a compound
B) with one PA and a compound C) with one FG (epoxy group) and one
SIL; a compound A) with two CTC, a compound B) with one PA and a
compound C) with one FG (unsaturated group) and one SIL.
Preferably, compounds A), B) and optionally C) are selected to give
a mixture of A), B) and optionally C) that is liquid at 21.degree.
C., 1 bar. Such mixture does not require additional solvents to
become liquid. For a liquid mixture of compounds A), B) and
optionally C) it is sufficient that at least one, preferably two of
the compounds A), B) and C) are liquid and thus are solvents for
the remaining solid compound A), B) or C).
The reaction between compounds A), B) and optionally C) starts
usually already at room temperature (about 20.degree. C.) and may
be completed at room temperature. The reaction may be supported by
increasing the temperature of the coating composition or sealant,
for example, up to 100.degree. C. Alternatively or in addition, any
activation energy for the reactions may be provided by high-energy
radiation such as visible or UV-light. It is an advantage of the
invention that the reaction easily occurs at low temperature and
does not require supply of significant further energy such as high
temperatures or high energy radiation.
Compounds A), B) or C) or any mixture thereof may comprise
additives, such as stabilizers such as biocides, catalysts or
additives that are desired or necessary for the intended final use
of the cross-linked polymer, for example, colorants such as
pigments. The catalysts include catalysts for the curing of the
silicon-functional group, notably Sn comprising catalysts.
Compounds A), B) or C) or any mixture thereof may comprise
solvents. In a preferred embodiment no solvent is required, see
above.
Preferably, the content of silicon in the polymer obtained by
reacting compound A), B) and optionally C) is 0.001 to 0.4 mol Si
per 100 g of the polymer, especially 0.001 to 0.3 mol Si per 100 g
of the polymer.
More preferably, the content of silicon in the polymer obtained by
reacting compound A), B) and optionally C) is 0.005 to 0.2 mol Si
per 100 g of the polymer.
Most preferably, the content of silicon in the polymer obtained by
reacting compound A), B) and optionally C) is 0.01 to 0.15 mol Si
per 100 g of the polymer.
The above content of Si applies to the polymer obtained in step b1)
as well as to the cross-linked polymer finally obtained by process
steps b1) and b2), or, alternatively, by process steps c1) to c2)
or by process steps d1) to d3).
Compounds A), B) and optionally C) are processed either by process
steps b1) to b2), or, alternatively, by process steps c1) to c2) or
by process steps d1) to d3).
The process of steps b1) to b2) is a two-step process. In process
step b1) compounds A) and B) and optionally C) are reacted to form
a polymer. Process step b1) is performed under exclusion of water.
To avoid any humidity process step b1) may be performed under inert
gas. The obtained polymer comprises silicon-functional groups that
are still curable by water, notably humidity.
In process step b2) the polymer obtained is brought into the
desired form, which is a coating, a filling or any other
three-dimensional body. The silicon-functional groups cross-link
with each other in the presence of any ambient water, for example,
humidity or water supplied. Usually the normal humidity is
sufficient to finally get a fully cross-linked polymer. The
cross-linking process may be accelerated by providing further
water. For example, water may be added to the polymer and the end
of step b1) shortly before starting step b2).
In process steps c1) to c2) the compounds are first brought into
the desired form, which is a coating, a filling or any other
three-dimensional body, followed by a step c2) which is one step
reaction including the formation of the polymer of A), B) and
optionally C) as described above and simultaneously including the
curing reaction of the silicon-functional groups. In process step
c2) no humidity must be avoided. Process step c2) may be
accelerated by providing further water.
In process step d1) to d3) curing of the silicon-functional groups
occurs first, followed by the formation of the polymer of compounds
A), B) and optionally C).
Therefore, the compound with the silicon-functional group, which
may be a compound A), B) or C), is brought into the desired form
and the silicon-functional groups are cured to give a silicon-based
network. The compound with the silicon-functional group may be used
in form of a mixture comprising any other compounds A), B) and C).
However, it has to be avoided that the mixture comprises any
combination of compounds A) and B). The mixture may comprise either
compounds A) or, alternatively, compounds B) but not both, as the
formation of the polymer of A), B) and optionally C) immediately
starts with the ring-opening reaction of the amino group of B) with
the monothiocarbonate group of A). In process steps d1) and d2) no
humidity must be avoided. Process step d2) may be accelerated by
providing further water.
The formation of the polymer of A), B) and C) follows in process
step d3) by adding the missing compound B) or, alternatively, the
missing compound A) to start the formation of the polymer. The
missing compound A) or B) may be used in form of a mixture
comprising compounds C).
Preferably, compounds A), B) and optionally C) are processed either
by process steps b1) to b2), or, alternatively, by process steps
c1) to c2).
More preferably, compounds A), B) and optionally C) are processed
by process steps b1) to b2).
The coatings, fillings or other three-dimensional bodies obtained
either by process steps b1) to b2), or, alternatively, by process
steps c1) to c2) or by process steps d1) to d3) are fully cured and
have good mechanical properties such as hardness and stiffness.
The process is useful to obtain coatings, a sealed material or a
three-dimensional body for any technical application or any other
purpose.
The process is useful for decorative, protective or functional
coatings.
The process is useful for paints and lacquers which usually have
the dual use to protect the substrate coated and to be
decorative.
The process is useful for functional coatings which have the
purpose to change or improve the surface properties of a substrate
or to protect the surface of a substrate, for example, to improve
adhesion, wettability, corrosion resistance or wear resistance.
Functional coatings on fibers are often used as compatibilizers to
improve interaction or adhesion between the polymer matrix and
fibers in composites.
With the process of this invention silyl-modified polymers with
urethane and sulfur functionality are obtained easily and
economically. The process may be performed at room temperature
without further supply of energy. The process does not require the
use of isocyanates or starting materials with mercaptan groups. The
process offers the possibility to prepare a variety of products,
notably hybrid products having the benefits resulting from the
content of sulfur, urethane and silyl cross-linking, which are, for
example, mechanical properties in combination with chemical
resistance, barrier properties, anti-static and anti-corrosion
properties.
Compounds of formula (IV), for example,
5-(3-trimethoxysilylpropoxymethyl)-1,3-oxathiolane-2-one, provide a
suitable alternative to known silanes such as
trimethoxysilylalkyl-glycidylether which are well-known to form a
siloxane network at ambient atmosphere.
Compounds of formula (IV) provide further the advantage, that a
nucleohil reaction partner may selectively react with the cyclic
monothiocarbonate unit allowing the release of the SH-functionality
which offers a broad variety of follow-up reactions. Compound of
formula (IV) may thus be employed as a chain extender rather than a
reactive monomer.
Thus, compounds of formula (IV) represent a new building block for
the synthesis of especially high molecular compounds and polymers.
They may react as chain extender as well as allow a curing
mechanism via siloxane linkages in orthogonal direction. Thus, an
additional siloxane compound is not necessary. In case of employing
amines as nucleophiles the reaction yields a valuable
silane-functionalized urethane compound.
EXAMPLES
Following compounds have been used in the examples:
Compound A:
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)]
(BDO-CTC, prepared according unpublished application
PCT/EP2019/081639), of formula:
##STR00012##
5-(Methacryloyloxy)methyl-1,3-oxathiolane-2-one (MMA-CTC, prepared
according to Example 8 of WO 2019/034469 A1) of formula
##STR00013##
Compound B:
Butylamine
1,3-Bis(aminomethyl)cyclohexane (BAC) of formula
##STR00014## 3-Aminopropyl-trimethoxysilane (APTMS)
Compound C: Trimethoxysilylpropyl methacrylate (CAS 2530-85-0)
Trimethoxysilylpropyl glycidylether
(3-(3-glycidyloxypropyl)trimethoxysilane (CAS 2530-83-8)
Trimethylolpropane trimethacrylate (TMPTMA, CAS 3290-92-4)
Bisphenol-A-glycerolate-dimethylacrylate (CAS 1565-94-2)
Diurethane-dimethacrylate (diurethane-DMA, CAS 72869-86-4)
Example 1: BDO-CTC+3-aminopropyl-trimethoxysilane+TMPTMA
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] (5
g) and TMPTMA (1.75 g) were mixed under stirring at room
temperature. Subsequently, 3-aminopropyl-trimethoxysilane (5.5 g)
was added, and stirring was continued for additional 3 min at room
temperature, increasing viscosity over time. One part of the
reaction mixture was transferred to a coating application via
doctor blade (60 .mu.m thickness) using various substrates (glass,
steel). The other part of the reaction mixture was transferred to a
cylindrical mold (diameter: 45 mm) and kept at ambient conditions.
After 60 hours the second sample was cured yielding a hard and
brittle specimen with uneven surface.
The coating proved to be completely dry after 1 hour at room
temperature.
Example 2: BDO-CTC+BAC+trimethoxysilylpropyl methacrylate
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] (5
g) and 3-(trimethoxysilyl)-propyl methacrylate (7.7 g) were mixed
under stirring at room temperature. Subsequently,
1,3-bis(aminomethyl)cyclohexane (2.2 g) was added, and stirring was
continued for additional 3 min at room temperature showing an
increase in temperature and viscosity. 5.5 g of the mixture were
subsequently transferred to a cylindrical mold (diameter: 45 mm)
and kept at ambient conditions. After 1 hour the sample showed
skinning at the surface. The sample was completely cured overnight.
The specimen showed significant shrinkage and hardness.
Example 3: BDO-CTC+BAC+trimethoxysilylpropyl glycidylether
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] (5
g) and trimethoxysilylpropyl glycidylether (7.3 g) were mixed under
stirring at room temperature. Subsequently,
1,3-bis(aminomethyl)cyclohexane (2.2 g) was added, and stirring was
continued for additional 3 min at room temperature showing an
increase in temperature and viscosity. 5.5 g of the mixture were
subsequently transferred to a cylindrical mold (diameter: 45 mm)
and kept at ambient conditions. The sample showed skinning after 1
hour; after 5 hours the sample was nearly cured. The sample was
completely cured over night. The transparent and flexible polymer
showed flexibility and moderate brittleness
Example 4: BDO-CTC+butylamine+trimethoxysilylpropyl
glycidylether
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] [5
g] and trimethoxysilylpropyl glycidylether (7.3 g) were mixed under
stirring at room temperature. Subsequently, butylamine (2.26 g) was
added, and stirring was continued for additional 3 min at room
temperature showing an increase in temperature and viscosity. 5.5 g
of the mixture were subsequently transferred to a cylindrical mold
(diameter: 45 mm) and kept at ambient conditions. After 1 hour the
sample showed skinning at the surface on top of the still viscous
sample. The sample was completely cured within 58 hours at ambient
conditions. The specimen was very brittle.
Example 5: BDO-CTC+butylamine+trimethoxysilylpropyl
methacrylate
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] (5
g) and 3-(trimethoxy-silyl)propyl methacrylate (7.7 g) were mixed
under stirring at room temperature. Subsequently, butylamine (2.26
g) was added, and stirring was continued for additional 3 min at
room temperature showing an increase in temperature and viscosity.
5.5 g of the mixture were subsequently transferred to a cylindrical
mold (diameter: 45 mm) and kept at ambient conditions. After 1 hour
the sample showed skinning at the surface on top of still viscous
sample. The sample was completely cured within 60 hours at ambient
conditions. The specimen was very brittle.
Example 6: BDO-CTC+BPA-Gly-DMA+1,3-BAC+APTMS
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] (5
g) and bisphenol-A-glycerolate-dimethylacrylate (7.95 g) were mixed
under stirring at room temperature. Subsequently, a mixture of
1,3-bis(aminomethyl)cyclohexane (1.1 g) and
3-aminopropyl-trimethoxysilane (2.78 g) was added under stirring.
The mixture was homogenized, and stirring was continued at ambient
conditions. The mixture increased in viscosity, and after 3 min the
mixture was applied as a coating on steel via a doctor blade (60
.mu.m thickness). The sample was kept at ambient temperature. After
60 min the coating showed surface skinning; the sample was
completely cured within 24 hours at ambient conditions. The
crosshatch test revealed excellent adhesion to the surface.
The content of silicon in the coated polymer was 0.1 mol Si/100 g
polymer.
The silicon content (in mol) was calculated based on the used
amounts of the starting materials, i.e., as silicon/total weight of
the starting materials.
Example 7: BDO-CTC+MMA-CTC+Diurethane-DMA+APTMS+BAC
Bis-1,3-oxathiolane-2-one-5,5'-[1,4-butanediylbis(oxymethylene)] (5
g) and diurethane-dimethylacrylate (7.2 g) were mixed under
stirring at room temperature followed by addition of
5-(methacryloyloxy)methyl-1,3-oxathiolane-2-one (2.0 g).
Subsequently, a mixture of 1,3-bis(aminomethyl)cyclohexane (2.2 g)
and 3-aminopropyl-trimethoxysilane (1.76 g) was added under
stirring. The mixture was homogenized, and stirring was continued
at ambient conditions. The mixture increased in viscosity, and
after 3 min the mixture was applied as a coating on steel via a
doctor blade (60 .mu.m thickness). The sample was kept at ambient
temperature. The coating was completely cured within 24 hours at
ambient conditions.
The content of silicon in the coated polymer was 0.054 mol Si/100 g
polymer.
Example 8: Synthesis of the Compounds of Formula (IV)
Compounds of formula (IV) may be prepared in accordance with the
process described in WO 2019/034469 A1.
The compound of formula
##STR00015##
was prepared in two steps as follows:
First step: Synthesis of
[1-(chloromethyl)-2-(3-trimethoxysilylpropoxy)ethyl]
carbonochloridate
A 0.25 L stirred tank glass reactor equipped with two condensers
(-30.degree. C. and -78.degree. C. (dry ice)) phosgene dip pipe and
internal thermometer was purged with dry nitrogen overnight.
Afterwards 113.6 g (0.47 mol, 1.00 eq.) of
3-glycidoxypropyltrimethoxysilane were introduced under nitrogen
atmosphere. The cooling of the tank reactor was turned on and was
adjusted to 15.degree. C. After the reactor reached this
temperature, 1.30 g (0.005 mol, 1.00 mol %) of tetrabutylammonium
chloride (TBACl) were suspended in the starting material.
Afterwards phosgene (overall 61 g, 0.67 mol, 1.31 eq.) was added to
the reactor via the dip pipe. The temperature of the reaction
mixture was continuously monitored and was kept below 20.degree. C.
by carefully adjusting the rate of the phosgene addition. Overall
the addition took approximately 4 hours. After the phosgene
addition was completed the initial cooling of the reactor was
turned off, and the reactor was allowed to slowly reach room
temperature. Afterwards the reaction mixture was stirred at room
temperature for further 2 hours. Finally, the reaction mixture was
stripped, with dry argon at room temperature, phosgene-free within
4 hours. The resulting colorless oil (151 g, 0.45 mol, 96% yield,
regioisomeric purity: >95%) was directly used, without further
purification, for the thiocarbonate formation.
Second step: Synthesis of
5-(3-trimethoxysilylpropoxymethyl)-1,3-oxathiolane-2-one
[1-(chloromethyl)-2-(3-trimethoxysilylpropoxy)ethyl]
carbonochloridate (20 g, 0.06 mol) and acetonitrile (50 mL) were
placed in a 250 mL 4 neck round bottom flask equipped with a KPG
crescent stirrer, dropping funnel, thermometer and a reflux
condenser. The solution was cooled down to 0.degree. C. with an ice
bath before solid Na.sub.2S (1 eq.) was slowly added, maintaining
the temperature at 5.degree. C. After the complete addition the ice
bath was removed, and the reaction mixture was allowed to warm to
room temperature. After stirring for 4 hours the suspension was
filtered, and the solvent was removed under reduced pressure. The
crude cyclic thiocarbonate was obtained as a clear oil (17 g,
95%).
* * * * *